CN110105553A - Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof - Google Patents
Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof Download PDFInfo
- Publication number
- CN110105553A CN110105553A CN201910270363.XA CN201910270363A CN110105553A CN 110105553 A CN110105553 A CN 110105553A CN 201910270363 A CN201910270363 A CN 201910270363A CN 110105553 A CN110105553 A CN 110105553A
- Authority
- CN
- China
- Prior art keywords
- itaconic acid
- hyperbranched poly
- resin
- preparation
- curing resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005989 resin Polymers 0.000 title claims abstract description 97
- 239000011347 resin Substances 0.000 title claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000003848 UV Light-Curing Methods 0.000 title claims abstract description 60
- -1 Ester modified itaconic acid Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 47
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 230000032050 esterification Effects 0.000 claims abstract description 30
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 22
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 230000004044 response Effects 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000004321 preservation Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940120693 copper naphthenate Drugs 0.000 claims description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 2
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 23
- 239000000853 adhesive Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- 239000002028 Biomass Substances 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OYBSKKHHESSJOP-UHFFFAOYSA-N 2-methylidene-3-oxobutanedioic acid Chemical class OC(=O)C(=C)C(=O)C(O)=O OYBSKKHHESSJOP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009975 flexible effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000218195 Lauraceae Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof, the solidified resin is mainly prepared from the following raw materials: itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy acrylate, esterification catalyst, polymerization inhibitor, polycondensation catalyst, stabilizer, neutralizer and water.The preparation method is that: (1) itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy acrylate, esterification catalyst and polymerization inhibitor are mixed, under nitrogen protection, heating reaction, heat preservation Depressor response cools down to being no longer discharged and stopping reacting；(2) polycondensation catalyst and stabilizer, heating under reduced pressure reaction is added, cooling is added neutralizer, adds water,.Solidified resin of the present invention is of light color, and curing rate is fast, and hardness is high, adhesive force, flexibility and water-tolerant, and biomass content is high, environmentally protective；The method of the present invention is simple, and preparation process is solvent-free, at low cost, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of light-cured resins and preparation method thereof, and in particular to a kind of ester modified itaconic acid of hyperbranched poly
Base water borne UV curing resin and preparation method thereof.
Background technique
The water-borne UV-curing resin-bonded plurality of advantages of UV curing technology and aqueous technology, with traditional UV solidified resin phase
Than water-borne UV-curing Resin Rheology is easy to control, easy for construction；It is not required to addition reactive diluent, VOC emission amount is low；Belong to height
Molecular weight aqueous dispersion, and do not have to consider its viscosity problem, to solve light solidifying coating high rigidity and high-flexibility cannot
The problem combined.It may be said that the excellent properties of water-borne UV-curing resin have widened the application field of UV curing technology.However,
Existing water-borne UV-curing resin is mainly prepared by petrochemical material, increasingly depleted with fossil resources, also just inevitable
The cost increase for making water-borne UV-curing resin.
With the enhancing of people's environmental consciousness, it is solid to prepare aqueous UV that fossil resources are substituted using biomass renewable resource
Change resin and obtains the extensive concern of people.The report for preparing water-borne UV-curing resin using biomass is more, is to utilize mostly
Vegetable oil preparation, it is so sharp et al. using epoxidized soybean oil as raw material, it is double that acrylic acid is connected to epoxy group open loop using acrylic acid
Key, then reacted through maleic anhydride with hydroxyl and connect carboxyl, it neutralizes and deionized water is added later, it is solid to obtain the aqueous UV of epoxy soybean oil base
Change resin, still, products therefrom color is deep, and curing rate is slow, hardness of film it is low (Xu Rui, the modified product based on soybean oil
Research [D] Xiamen University, 2009).
Itaconic acid can industrially be produced by way of biofermentation, be a kind of important natural reproducible resource.Clothing
Health acid contains unsaturated double-bond and two carboxyls in structure, has very active chemical property, addition reaction, ester can occur
Change reaction and polymerization reaction.But the document report about the water-borne UV-curing polyester of itaconic acid base is less.Jinyue Dai et al.
With itaconic acid and glycols esterifying polycondensation, neutralized addition deionized water obtains the aqueous UV resin of itaconic acid base, although products therefrom
Hardness of film is high, and adhesive force is good, and still, coloured product is deep, and slow (the Progress in Organic of curing rate
Coatings, 2015,78:49-54.).Based on this research, Jinyue Dai et al. using epoxy soybean oil acrylate with
The water-borne UV-curing resin of itaconic acid base is compounded, and the aqueous UV resin of high-performance biomass is prepared for, although film performance is excellent,
But coloured product is deep, and unstable, will be layered in a few houres (Green Chemistry, 2015,17:2383-
2392.).
CN106750221B discloses a kind of aqueous UV resin of epoxy acrylate modification by copolymerization furoate clothing base, is aqueous
Epoxy acrylic resin is introduced in itaconic acid base polyester resin.Although the introducing of epoxy acrylic resin can be good at accelerating tree
The laser curing velocity of rouge, the more original resin of the comprehensive performance of resin greatly improve, but the addition of rigid epoxy resin is so that flexible
Property decline, while the presence of internal stress improves its adhesive force also well.
CN105440252B discloses a kind of ultraviolet light solidfication water polyurethane modified epoxy itaconic acid resin and its preparation
Method is made by epoxy resin, itaconic acid, polyglycols, diisocyanate.But the preparation process of this method is complicated, and main
Photocuring effect is carried out by the double bond of itaconic acid, relative to the double bond of acrylic-type, laser curing velocity is relatively low.
CN105061727B discloses a kind of UV-curable water-borne epoxy itaconic acid resin and preparation method thereof, basic
Raw material is epoxy resin, itaconic acid and epoxide diluent, and ultraviolet curing group is the double bond of itaconic acid.But tree obtained by this method
The flexibility and laser curing velocity of rouge be not all good enough.
CN107090240A discloses a kind of preparation method of photocuring itaconic acid modified alkyd resin coating, still, should
Alkyd resin obtained by method haves the defects that hardness of film is not high, and due to the presence of organic solvent, loses photocureable coating
Environmentally protective advantage.
Therefore, in the water borne UV curing resin technology of preparing of existing itaconic acid base, generally there are laser curing velocities and resin
The problem of flexibility can not be taken into account, although excessive itaconic acid declines in the presence of that can accelerate laser curing velocity, flexibility.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome drawbacks described above of the existing technology, provide it is a kind of of light color,
Curing rate is fast, and hardness is high, adhesive force, flexibility and water-tolerant, and biomass content is high, and environmentally protective hyper-branched polyester changes
Property itaconic acid base water borne UV curing resin.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of work
Skill is simple, and preparation process is solvent-free, at low cost, and the ester modified aqueous light of itaconic acid base of hyperbranched poly for being suitable for industrialized production is solid
Change the preparation method of resin.
The technical solution adopted by the present invention to solve the technical problems is as follows: the ester modified aqueous light of itaconic acid base of hyperbranched poly
Solidified resin is mainly prepared from the following raw materials: itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy acrylate,
Esterification catalyst, polymerization inhibitor, polycondensation catalyst, stabilizer, neutralizer and water.
Itaconic acid forms the basic skeleton structure of chain polyester by the polycondensation reaction with 1,4-butanediol, and provides and be used for
Cured double bond group and the carboxyl for Water-borne modification.
Hyperbranched poly ester polyol is a series of polymer for the highly branched structure that there are a large amount of activity hydroxies in ends, due to
Its unique branched molecular structure without entanglement between molecule, and contains a large amount of end group, therefore shows high-dissolvability, low
The property that many linear polymers such as viscosity, high chemical reactivity do not have.The end of hyperbranched poly ester polyol
With itaconic acid polycondensation reaction can occur for hydroxyl, suitably increase the degree of branching of system, and further increase molecular weight, can also increase
Add the content of photocuring activity double key, while utilizing its special spherical structure and internal cavity structures, makes it have interior soft outer
Hard performance plays the effect to the aqueous homogeneous toughening of UV resin, is that resin has bloom curing activity and excellent flexibility
Key factor.
Epoxy acrylate is used to provide the end position acrylic double bond of high activity, to improve curing rate, and introduces ring
The basic framework of oxypropylene acid esters, to improve the hardness and adhesive force of resin.
The effect of esterification catalyst is raising reaction speed, promotes the carry out degree of esterification.
The effect of polymerization inhibitor, which essentially consists in, inhibits the double bond in itaconic acid and epoxy acrylate to crosslink at high temperature
Reaction, leads to that gel occurs in polymerization process.
The effect of polycondensation catalyst is the further polycondensation reaction of promotion prepolymer, and the resin of synthesis is made to reach suitable
Molecular weight.
The effect of stabilizer is that gel occurs for prevention system, while anti-oxidant, reduces the color of resin.
Neutralizer generates carboxylate by reacting with the excessive carboxyl in synthetic resin, and resin is made to become water-dilutable
Resin.
Water is mainly used for the itaconic acid base polyester resin that certain solid content is prepared in dilution.
Preferably, the parts by weight of the ester modified each raw material of itaconic acid base water borne UV curing resin of the hyperbranched poly are as follows: clothing health
36~47 parts of acid, 15~24 parts of 1,4-butanediol, 2~6 parts of hyperbranched poly ester polyol, 2~6 parts of epoxy acrylate, esterification
It 0.3~0.8 part of catalyst, 0.2~0.5 part of polymerization inhibitor, 0.1~0.3 part of polycondensation catalyst, 0.1~0.4 part of stabilizer, neutralizes
7~14 parts of agent, 15~30 parts of water.The dosage of itaconic acid is more, and part itaconic acid may make up the intermediate skeleton structure of polyester, also
Part itaconic acid forms the carboxyl end group of resin, reacts for subsequent Water-borne modification.The introducing of epoxy acrylate mainly improves
The curing rate and hardness of resin, if dosage is excessive, synthetic resin viscosity is bigger than normal, is unfavorable for applying.If hyper-branched polyester
Dosage is excessive, and due to hyper-branched structure, resin is during the preparation process, it is prone to cross-linked gel reaction, it is difficult if dosage is very few
To play the effect of toughening modifying.
Preferably, the hyperbranched poly ester polyol is two generation molecules of Boltorn type polyester polyol.Boltorn type
Polyester polyol is according to raw material proportioning and polycondensation reaction condition, an available generation, the molecule in two generations to seven generations, wherein two generations produced
The theoretical terminal hydroxy group number of object is 8, and the terminal hydroxy group number of four generation molecules is 64, the internal cavities of the polyester polyol molecule of different algebra
It is of different sizes.Comprehensively consider preparation cost and terminal hydroxy group number and internal cavities size, the present invention has selected two generation hyper-branched polyesters
Polyalcohol is raw material.
Preferably, two generation molecules of the Boltorn type polyester polyol the preparation method comprises the following steps: by pentaerythrite, chain extension
Agent and esterification catalyst mixing, under nitrogen protection, after heating reaction, heat preservation Depressor response to being no longer discharged and stop reacting,
N-hexane washing of precipitate is added in products therefrom to purify >=2 times, vacuum drying,.
The synthetic route of two generation molecules of the Boltorn type polyester polyol is shown below.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the pentaerythrite and chain extender rub
You are than being 1:12.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the dosage of the esterification catalyst is to expand
The 0.4~0.8% of chain agent quality.
Under the consumption proportion of the pentaerythrite, chain extender and esterification catalyst, it is hyperbranched to be more advantageous to two generations of acquisition
Polyester polyol, that is, the super branched molecule structure that theoretical terminal hydroxy group number is 8 will lead to if dosage is excessive or very few
To the hyperbranched poly ester structure in the different generations such as a generation or three generations, it is unfavorable for the preparation of subsequent water borne UV curing resin.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the chain extender is dihydromethyl propionic acid
And/or dimethylolpropionic acid.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the esterification catalyst is to toluene sulphur
One or more of acid, sulfonate resin, the concentrated sulfuric acid, phosphoric acid or tin oxide etc..
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the temperature of the heating reaction is 120
~140 DEG C, the time is 0.5~1.5h.If reaction temperature is lower than 120 DEG C, esterification speed is too slow, if reaction temperature is more than
140 DEG C, then coloured product is deepened, it is difficult to obtain light-coloured prods.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, at 120~140 DEG C, vacuum degree 0.01
Under~0.04MPa, heat preservation Depressor response is to being no longer discharged and stop reacting.If vacuum degree is excessively high, raw material proportioning mistake will lead to
Weighing apparatus, polycondensation reaction aggravation, it is difficult to obtain the molecule of object algebra, and maintain under rough vacuum, need to only take away in reaction and generate
Water can.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the n-hexane and pentaerythrite expand
The mass ratio of chain agent and esterification catalyst quality sum is 1.5~2.5:1.
Preferably, in the preparation of two generation molecules of Boltorn type polyester polyol, the vacuum drying temperature be 70~
90 DEG C, vacuum degree is 0.05~0.08MPa, and the time is 1~2h.Under the drying condition, it is more advantageous to and removes as much as possible
N-hexane solvent and micro-moisture in hyper-branched polyester, are conducive to the preparation of subsequent water borne UV curing resin.
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the epoxy acrylate is E-44
The epoxy acrylate of type epoxy resin preparation and/or the epoxy acrylate of E-51 type epoxy resin preparation.The epoxy third
Olefin(e) acid ester can be marketable material, E-44 type or E-51 type epoxy resin epoxy group open loop can also be prepared by acrylic acid,
Preparation method is existing mature technology.
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the esterification catalyst is to toluene
One or more of sulfonic acid, sulfonate resin, the concentrated sulfuric acid, phosphoric acid or tin oxide etc..
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the polymerization inhibitor is hydroquinone, right
One or more of hydroxyanisol, p-tert-Butylcatechol or copper naphthenate etc..
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the polycondensation catalyst is two laurels
One or more of sour dibutyl tin, antimony glycol, germanium dioxide, aluminium chloride or butyl titanate etc..
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the stabilizer is phosphorous acid, phosphorous
One or more of triphenyl phosphate ester, diphenyl phosphite or ammonium phosphite etc..
Preferably, in the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, the neutralizer is triethylamine, three second
One or more of hydramine or ammonium hydroxide etc..
The present invention further solves technical solution used by its technical problem: the ester modified itaconic acid Ji Shui of hyperbranched poly
The preparation method of property light-cured resin, comprising the following steps:
(1) itaconic acid, 1,4- butanediol, hyperbranched poly ester polyol, epoxy acrylate, esterification catalyst and polymerization inhibitor are mixed
It closes, under nitrogen protection, after carrying out heating reaction, heat preservation Depressor response is to being no longer discharged and stop reacting, after being cooled to room temperature,
Obtain prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, carries out heating under reduced pressure reaction, cooling
Afterwards, neutralizer is added and adjusts pH value, finally plus water adjusts solid content, obtains the ester modified itaconic acid Ji Shuixingguangguhuashu of hyperbranched poly
Rouge.
The synthetic route of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly is shown below.
The present invention is with itaconic acid, 1,4- butanediol, hyperbranched poly ester polyol, epoxy acrylate, polymerization inhibitor, neutralizer
For raw material, the excess in the hydroxyl and itaconic acid in 1,4-butanediol, hyperbranched poly ester polyol and epoxy acrylate is utilized
Carboxyl participates in esterification, forms the basic skeleton structure of carboxyl end group, increases system degree of branching to improve molecular weight, connect height
Active end position acrylic double bond；Polymerization inhibitor is used to prevent double bond under the conditions of pyroreaction that polymeric gel occurs, then contracts through vacuum
Poly- reaction, increases the molecular weight of polymer；Neutralizer generates salt for reacting with remaining carboxyl, increases the water solubility of system,
Obtain the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly.
Preferably, in step (1), the temperature of the heating reaction is 120~140 DEG C, and the time is 0.5~1.5h.If anti-
Answer temperature too low, then esterification is incomplete, if reaction temperature is excessively high, coloured product is deepened and gel reaction easily occurs.
Preferably, in step (1), under 120~140 DEG C, 0.01~0.03MPa of vacuum degree, Depressor response is kept the temperature to not
It is discharged again and stops reacting.Decompression can remove the water generated in reaction process, and esterification can be made complete, if vacuum degree is excessive,
Easily raw material is extracted out, molecular weight of product reduction is eventually led to, influences curing rate and film performance, if vacuum degree is too small, remove
Water is ineffective, and influences the polycondensation reaction of next step.
Preferably, in step (2), the temperature of heating under reduced pressure reaction is 130~150 DEG C, vacuum degree is 0.08~
0.10MPa, time are 3~5h.If reaction temperature is excessively high, easily formed gel, if reaction temperature is too low, condensation degree of dissolved compared with
Low, molecular weight of product is small, so that curing rate reduces, film performance is deteriorated；If vacuum degree is excessive, easily small molecule prepolymer
Extraction is difficult to extract the water of polycondensation generation out if vacuum degree is too small.
Preferably, in step (2) ,≤85 DEG C are cooled to.Carboxylic acid amine salt can be generated in the temperature.
Preferably, in step (2), pH value is adjusted to 6.5~7.5.The pH value can guarantee that the resin of synthesis is neutrality, benefit
It is saved in stablizing.
Preferably, in step (2), water is added to adjust solid content to 70~85%.If solid content is excessively high, although curing and drying is fast
Degree is fast, and transportation and packing expense is low, but product viscosity increases, and is increased using difficulty, if solid content is too low, on the contrary, described solid
There is optimal comprehensive performance under content.
Beneficial effects of the present invention are as follows:
(1) the ester modified itaconic acid base water borne UV curing resin appearance color of hyperbranched poly of the present invention is shallow, and curing time is 5~12s,
Pencil hardness is 4~5H, and adhesive force is 0~1 grade, impregnates non-whitening after 48h in water, and flexibility is 4~5 grades, and film is comprehensive
It has excellent performance, compared with the prior art only the itaconic acid base water-borne UV-curing resin ester modified with epoxy acrylic, in solidification speed
In degree, pencil hardness and the comparable situation of water resistance, in adhesive force, the most important index of the two light-cured resins of flexibility
Be greatly improved, adhesive force is promoted by 3 grades of the prior art to 0~1 grade, flexibility by 2 grades of the prior art promoted to
Existing 4~5 grades, curing rate and flexibility have been taken into account well；
(2) biomass content of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly of the present invention is high, environmentally protective, can be wide
It is general to be applied to waterborne UV coating, aqueous UV paper oil polish etc., with good application prospect；
(3) the method for the present invention simple process, preparation process is not necessarily to organic solvent, at low cost, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the ester modified itaconic acid base water borne UV curing resin of 1 hyperbranched poly of the embodiment of the present invention and 1 itaconic acid of comparative example
The IR of the water-borne UV-curing resin of base compares spectrogram.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Epoxy acrylate used in the embodiment of the present invention is commercial product, is prepared by E-44 type epoxy resin；This hair
Raw material used in bright embodiment, comparative example or chemical reagent are obtained by routine business approach unless otherwise specified.
The preparation method reference example 1 of two generation molecules of type polyester polyol
By 6.8g pentaerythrite (0.05mol), 82.1g dihydromethyl propionic acid (mass content 98%, 0.6mol) and 0.4g to first
Benzene sulfonic acid mixes in there-necked flask, under nitrogen protection, at 130 DEG C, after heating reaction 1h, 130 DEG C, 0.03MPa it is true
Under reciprocal of duty cycle, the washing of precipitate of 200g n-hexane is added in products therefrom and mentions to being no longer discharged and stopping reacting for heat preservation Depressor response
Pure 3 times, under 80 DEG C, 0.06MPa vacuum degree, it is dried in vacuo 1h, obtains two generation molecules of Boltorn type polyester polyol.
The 1 aqueous UV of itaconic acid base of the ester modified itaconic acid base water borne UV curing resin Examples 1 to 5 of hyperbranched poly and comparative example
Resin
The parts by weight of each raw material are as shown in table 1:
The ester modified itaconic acid base water borne UV curing resin of 1 Examples 1 to 5 hyperbranched poly of table and
The list of ingredients of the aqueous UV resin of 1 itaconic acid base of comparative example
Note: "-" expression is not added in table.
The preparation method embodiment 1 of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly
(1) according to the raw materials and consumption of 1 embodiment 1 of table, by itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy third
Olefin(e) acid ester, esterification catalyst and polymerization inhibitor mix in there-necked flask, under nitrogen protection, at 130 DEG C, carry out heating reaction 1h
Afterwards, under 130 DEG C, 0.02MPa vacuum degree, Depressor response is kept the temperature to being no longer discharged and stopping reacting, after being cooled to room temperature, is obtained pre-
Condensation polymer；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, in 140 DEG C, 0.09MPa vacuum degree
Under, it carries out heating under reduced pressure and reacts 4h, after being cooled to 80 DEG C, neutralizer is added and adjusts pH value to 7.0, finally plus water adjusts solid content
To 80%, the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly is obtained.
As shown in Figure 1,3390cm-1The broad peak at place is the stretching vibration peak of-OH in resin, compared to comparative example 1, embodiment
1 hydroxyl peak is reinforced, this is when hyper-branched polyester is polyalcohol modified in the presence of the result of a large amount of unreacted terminal hydroxy groups；2926cm-1
It is-CH in polyester2Stretching vibration peak, due in hyper-branched polyester there are a large amount of methylene groups, it is real compared to comparative example 1
Apply-CH in example 12Stretching vibration peak also greatly increase, illustrate hyperbranched poly ester structure be copolymerized to synthesis resin in；
1728cm-1It is the stretching vibration absworption peak of C=O in unsaturated polyester (UP)；1635cm-1And 819cm-1It is the stretching vibration peak of double bond,
Illustrate the double bond that itaconic acid and epoxy acrylate are introduced in resin；1580 cm-1For phenyl ring skeleton structure in epoxy resin
Absorption peak；1508 cm-1It is the bending shock absorption peak that benzene ring structure contraposition replaces in epoxy resin, this illustrates the resin of synthesis
In be copolymerized epoxy acrylate.
The preparation method embodiment 2 of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly
(1) according to the raw materials and consumption of 1 embodiment 2 of table, by itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy third
Olefin(e) acid ester, esterification catalyst and polymerization inhibitor mix in there-necked flask, under nitrogen protection, at 120 DEG C, carry out heating reaction
After 1.5h, under 120 DEG C, 0.03MPa vacuum degree, heat preservation Depressor response is to being no longer discharged and stop reacting, after being cooled to room temperature,
Obtain prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, in 150 DEG C, 0.08MPa vacuum degree
Under, it carries out heating under reduced pressure and reacts 3.5h, after being cooled to 75 DEG C, neutralizer is added and adjusts pH value to 7.5, finally plus water adjusting contains admittedly
Amount obtains the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly to 83%.
The preparation method embodiment 3 of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly
(1) according to the raw materials and consumption of 1 embodiment 3 of table, by itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy third
Olefin(e) acid ester, esterification catalyst and polymerization inhibitor mix in there-necked flask, under nitrogen protection, at 140 DEG C, carry out heating reaction
After 0.5h, under 140 DEG C, 0.02MPa vacuum degree, heat preservation Depressor response is to being no longer discharged and stop reacting, after being cooled to room temperature,
Obtain prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, in 145 DEG C, 0.09MPa vacuum degree
Under, it carries out heating under reduced pressure and reacts 3h, after being cooled to 80 DEG C, neutralizer is added and adjusts pH value to 6.5, finally plus water adjusts solid content
To 84.9%, the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly is obtained.
The preparation method embodiment 4 of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly
(1) according to the raw materials and consumption of 1 embodiment 4 of table, by itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy third
Olefin(e) acid ester, esterification catalyst and polymerization inhibitor mix in there-necked flask, under nitrogen protection, at 130 DEG C, carry out heating reaction
After 1.5h, under 130 DEG C, 0.03MPa vacuum degree, heat preservation Depressor response is to being no longer discharged and stop reacting, after being cooled to room temperature,
Obtain prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, in 145 DEG C, 0.095MPa vacuum degree
Under, it carries out heating under reduced pressure and reacts 3.5h, after being cooled to 70 DEG C, neutralizer is added and adjusts pH value to 7.5, finally plus water adjusting contains admittedly
Amount obtains the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly to 80.8%.
The preparation method embodiment 5 of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly
(1) according to the raw materials and consumption of 1 embodiment 5 of table, by itaconic acid, 1,4-butanediol, hyperbranched poly ester polyol, epoxy third
Olefin(e) acid ester, esterification catalyst and polymerization inhibitor mix in there-necked flask, under nitrogen protection, at 135 DEG C, carry out heating reaction 1h
Afterwards, under 135 DEG C, 0.025MPa vacuum degree, Depressor response is kept the temperature to being no longer discharged and stopping reacting, after being cooled to room temperature, is obtained
Prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, in 135 DEG C, 0.085MPa vacuum degree
Under, it carries out heating under reduced pressure and reacts 4h, after being cooled to 85 DEG C, neutralizer is added and adjusts pH value to 6.5, finally plus water adjusts solid content
To 72%, the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly is obtained.
Comparative example 1
This comparative example is prepared according to technical method disclosed in CN106750221B embodiment 1.
Through detecting, the pH value of the water-borne UV-curing resin of gained itaconic acid base is 7.4, solid content 81.0%.
Respectively in 1 itaconic acid base of the ester modified itaconic acid base water borne UV curing resin of Examples 1 to 5 hyperbranched poly and comparative example
In water-borne UV-curing resin, water-soluble photoinitiator Irgacure 2959 is added with 3% mass ratio, it is solid in UV after being uniformly dispersed
Under change machine, ultraviolet light solidification (ultraviolet light condition of cure are as follows: curing power is 2kw, and sample is at a distance from ultraviolet lamp is carried out
20cm), then film performance test is carried out；Wherein, the detection method of product appearance is range estimation, the detection method standard of curing time
For GB/T 1728-1979, the detection method standard of pencil hardness is GB/T 6739-1996, the detection method standard of adhesive force
Detection method standard for GB/T 9286-1998, water resistance is GB/T 1733-1993, and flexible detection method standard is
GB/T 1731-1993, test result are as shown in table 2.
The ester modified itaconic acid base water borne UV curing resin of 2 Examples 1 to 5 hyperbranched poly of table and
The film performance test result contrast table of the 1 water-borne UV-curing resin of itaconic acid base of comparative example
As shown in Table 2, the ester modified itaconic acid base water borne UV curing resin appearance color of hyperbranched poly of the present invention is shallow, and curing time is
5~12s, pencil hardness are 4~5H, and adhesive force is 0~1 grade, impregnate non-whitening after 48h in water, and flexibility is 4~5 grades, are applied
Film excellent combination property, be compared with the prior art example 1 preparation the water-borne UV-curing resin of itaconic acid base compare, curing time,
Under pencil hardness and the comparable situation of water resistance, have in adhesive force, the most important index of the two light-cured resins of flexibility
Very big progress, adhesive force are promoted by 3 grades of comparative example 1 to 0~1 grade, and flexibility is promoted by 2 grades of comparative example 1 to existing
4~5 grades, taken into account curing rate and flexibility well.This illustrates the introducing of hyperbranched poly ester polyol, due to its presence
Special internal cavity structures realize the homogeneous toughening of modified resin, when reducing photocuring caused by internal stress well
Adhesive force decline, improves its adhesive force.
Claims (9)
1. a kind of ester modified itaconic acid base water borne UV curing resin of hyperbranched poly, which is characterized in that be mainly prepared from the following raw materials:
Itaconic acid, 1,4- butanediol, hyperbranched poly ester polyol, epoxy acrylate, esterification catalyst, polymerization inhibitor, polycondensation catalyst,
Stabilizer, neutralizer and water.
2. the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly according to claim 1, which is characterized in that described each
The parts by weight of raw material are as follows: 36~47 parts of itaconic acid, 15~24 parts of 1,4-butanediol, 2~6 parts of hyperbranched poly ester polyol, epoxy
2~6 parts of acrylate, 0.3~0.8 part of esterification catalyst, 0.2~0.5 part of polymerization inhibitor, 0.1~0.3 part of polycondensation catalyst, surely
Determine 0.1~0.4 part of agent, 7~14 parts of neutralizer, 15~30 parts of water.
3. the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly according to claim 1 or claim 2, it is characterised in that: institute
State the two generation molecules that hyperbranched poly ester polyol is Boltorn type polyester polyol.
4. the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly according to claim 3, it is characterised in that: described
Two generation molecules of Boltorn type polyester polyol the preparation method comprises the following steps: by pentaerythrite, chain extender and esterification catalyst mix,
Under nitrogen protection, heating reaction after, keep the temperature Depressor response to being no longer discharged and stopping reacting, be added in products therefrom just oneself
Alkane washing of precipitate purifies >=2 times, vacuum drying,.
5. the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly according to claim 4, it is characterised in that: the season
The molar ratio of penta tetrol and chain extender is 1:12；The dosage of the esterification catalyst is the 0.4~0.8% of chain extender quality；It is described
Chain extender is dihydromethyl propionic acid and/or dimethylolpropionic acid；The esterification catalyst is p-methyl benzenesulfonic acid, sulfonate resin, dense
One or more of sulfuric acid, phosphoric acid or tin oxide；It is described heating reaction temperature be 120~140 DEG C, the time be 0.5~
1.5h；Under 120~140 DEG C, 0.01~0.04MPa of vacuum degree, heat preservation Depressor response is to being no longer discharged and stop reacting；It is described
The mass ratio of n-hexane and pentaerythrite, chain extender and esterification catalyst quality sum is 1.5~2.5:1；The vacuum drying
Temperature be 70~90 DEG C, vacuum degree be 0.05~0.08MPa, the time be 1~2h.
6. the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly described according to claim 1~one of 5, feature exist
In: the epoxy acrylate is epoxy acrylate and/or the E-51 type epoxy resin preparation of E-44 type epoxy resin preparation
Epoxy acrylate；The esterification catalyst is one in p-methyl benzenesulfonic acid, sulfonate resin, the concentrated sulfuric acid, phosphoric acid or tin oxide
Kind is several；The polymerization inhibitor is one of hydroquinone, p-hydroxyanisole, p-tert-Butylcatechol or copper naphthenate
Or it is several；The polycondensation catalyst is dibutyl tin dilaurate, antimony glycol, germanium dioxide, aluminium chloride or butyl titanate
One or more of；The stabilizer is one of phosphorous acid, triphenyl phosphite, diphenyl phosphite or ammonium phosphite
Or it is several；The neutralizer is one or more of triethylamine, triethanolamine or ammonium hydroxide.
7. a kind of preparation side of the ester modified itaconic acid base water borne UV curing resin of the hyperbranched poly as described in one of claim 1~6
Method, which comprises the following steps:
(1) itaconic acid, 1,4- butanediol, hyperbranched poly ester polyol, epoxy acrylate, esterification catalyst and polymerization inhibitor are mixed
It closes, under nitrogen protection, after carrying out heating reaction, heat preservation Depressor response is to being no longer discharged and stop reacting, after being cooled to room temperature,
Obtain prepolycondensate；
(2) in the prepolycondensate obtained by step (1), polycondensation catalyst and stabilizer is added, carries out heating under reduced pressure reaction, cooling
Afterwards, neutralizer is added and adjusts pH value, finally plus water adjusts solid content, obtains the ester modified itaconic acid Ji Shuixingguangguhuashu of hyperbranched poly
Rouge.
8. the preparation method of the ester modified itaconic acid base water borne UV curing resin of hyperbranched poly according to claim 7, feature
Be: in step (1), the temperature of the heating reaction is 120~140 DEG C, and the time is 0.5~1.5h；At 120~140 DEG C, very
Under 0.01~0.03MPa of reciprocal of duty cycle, heat preservation Depressor response is to being no longer discharged and stop reacting.
9. special according to the preparation method of the ester modified itaconic acid base water borne UV curing resin of the hyperbranched poly of claim 7 or 8
Sign is: in step (2), the temperature of the heating under reduced pressure reaction is 130~150 DEG C, and vacuum degree is 0.08~0.10MPa, when
Between be 3~5h；It is cooled to≤85 DEG C；PH value is adjusted to 6.5~7.5；Water is added to adjust solid content to 70~85%.
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